Treatment of textile product for imparting water and oil repellency

ABSTRACT

A textile having sufficient water repellency, oil repellency and soil releasability before and after cleaning can be prepared by a method of preparing a treated textile has the steps of (1) preparing a treatment liquid containing a water- and oil-repellent agent and a stain blocking agent, (2) bringing the pH of the treatment liquid to at most 7, (3) applying the treatment liquid to the textile, (4) thermally treating the textile with steam, and (5) washing the textile with water and dehydrating the textile, wherein the water- and oil-repellent agent has a combination of (A) a fluorine-containing polymer comprising a repeat unit derived from vinyl chloride and/or vinylidene chloride, and (B) a fluorine-containing polymer free from a repeat unit derived from vinyl chloride and/or vinylidene chloride.

FIELD OF THE INVENTION

[0001] The present invention relates to a treatment for imparting waterrepellency, oil repellency, soil releasability and durability thereof toa textile. A method of the present invention is particularly useful forcarpet.

RELATED ART

[0002] Hitherto, various treatment methods have been proposed in orderto impart water repellency, oil repellency and soil releasability to atextile such as a carpet. For example, a process of treating a textilecomprising decreasing the pH of a treatment liquid, applying thetreatment liquid to the textile, thermally treating the textile withsteam, washing the textile with water, and dehydrating the textile(hereinafter, sometimes referred to as “Exhaust process”) is proposed.

[0003] A method comprising the Exhaust process is proposed in U.S. Pat.Nos. 5,073,442, 5,520,962 and 5,516,337, and International PublicationWO 98/50619.

[0004] U.S. Pat. No. 5,073,442 discloses a method of treating a textile,comprising conducting an Exhaust process by using a water- andoil-repellent agent comprising a fluorine-containing compound, aformaldehyde condensation product and an acrylic polymer. U.S. Pat. No.5,520,962 discloses a method of treating a carpet, comprising conductingan Exhaust process by using a fluorine-containing compound and apolymeric binder. U.S. Pat. No. 5,516,337 discloses a method of treatinga textile, comprising conducting an Exhaust process by using afluorine-containing water- and oil-repellent agent and a metal compoundsuch as aluminum sulfate. International Publication WO 98/50619discloses a method of treating a carpet, comprising conducting anExhaust process by using a fluorine-containing water- and oil-repellentagent and a salt such as a magnesium salt.

[0005] Sufficient water repellency, oil repellency and soilreleasability cannot be obtained by conducting the Exhaust process inaccordance with these methods.

SUMMARY OF THE INVENTION

[0006] An object of the present invention is to give a textile excellentin water repellency, oil repellency, soil releasability and durabilitythereof, when an Exhaust process is conducted with using a water- andoil-repellent agent having a specified composition.

[0007] The present invention provides a method of treating a textile,comprising steps of:

[0008] (1) preparing a treatment liquid comprising a water- andoil-repellent agent,

[0009] (2) adjusting pH of the treatment liquid to at most 7, preferablyat most 2,

[0010] (3) applying the treatment liquid to the textile,

[0011] (4) thermally treating the textile with steam, and

[0012] (5) washing the textile with water and dehydrating the textile,

[0013] wherein the water- and oil-repellent agent comprises acombination of (A) a fluorine-containing polymer comprising a repeatunit derived from vinyl chloride and/or vinylidene chloride, and (B) afluorine-containing polymer free from a repeat unit derived from vinylchloride and/or vinylidene chloride.

[0014] The present invention also provides a textile prepared by theabove-mentioned method.

DETAILED DESCRIPTION OF THE INVENTION

[0015] The procedure used in the present invention is an Exhaust processwhich comprises decreasing the pH of the treatment liquid comprising thefluorine-containing polymer, applying the treatment liquid to thetextile, washing the textile with water, and dehydrating the textile.

[0016] In the step (1) of the method of the present invention, thetreatment liquid comprising the water- and oil-repellent agent, which isapplied to the textile, is prepared. The treatment liquid comprising thewater- and oil-repellent agent may be in the form of a solution or anemulsion, particularly an aqueous emulsion.

[0017] In the step (2) in the method of the present invention, the pH ofthe treatment liquid is brought to at most 7. The pH of the treatmentliquid is preferably at most 3, more preferably at most 2. The pH can bedecreased by addition of an acid, such as an aqueous solution ofcitrconic acid and an aqueous solution of sulfamic acid, to thetreatment liquid.

[0018] In the step (3) of the method of the present invention, thetreatment liquid is applied to the textile. The water- and oil-repellentagent can be applied to a substrate to be treated (that is, the textile)by a know procedure. The application of the treatment liquid can beconducted by immersion, spraying and coating. Usually, the treatmentliquid is diluted with an organic solvent or water, and is adhered tosurfaces of the substrate by a well-known procedure such as an immersioncoating, a spray coating and a foam coating to a fabric (for example, acarpet cloth), a yarn (for example, a carpet yarn) or an original fiber.If necessary, the treatment liquid is applied together with a suitablecrosslinking agent, followed by curing. It is also possible to addmothproofing agents, softeners, antimicrobial agents, flame retardants,antistatic agents, paint fixing agents, crease-proofing agents, etc. tothe treatment liquid. The concentration of the water- and oil-repellentagent active component (that is, the fluorine-containing polymer) in thetreatment liquid contacted with the substrate may be from 0.05 to 10% byweight. The stain blocking agent may be used in the concentration of,for example, 0 to 1,000 parts by weight, particularly 1 to 500 parts byweight, in terms of the solid content, based on 100 parts by weight ofthe fluorine-containing polymer.

[0019] In the step (4) of the method of the present invention, thetextile is thermally treated. The thermal treatment can be conducted byapplying a steam (for example, 90° C. to 110° C.) to the textile under anormal pressure for e.g., 10 seconds to 10 minutes.

[0020] In the step (5) of the method of the present invention, thetextile is washed with water and dehydrated. The thermally treatedtextile is washed with water at least once. Then, in order to removeexcess water, the textile is dehydrated by a usual dehydration proceduresuch as a centrifuging and vacuuming procedure.

[0021] After the step (5), the textile can be dried.

[0022] The water- and oil-repellent agent used in the present inventioncomprises two fluorine-containing polymers, that is, thefluorine-containing polymer (A) and the fluorine-containing polymer (B).

[0023] The fluorine-containing polymer (A) is the fluorine-containingpolymer comprising a repeat unit derived from vinyl chloride and/orvinylidene chloride. The fluorine-containing polymer (B) is thefluorine-containing polymer free from a repeat unit derived from vinylchloride and/or vinylidene chloride.

[0024] The fluorine-containing polymers (A) and (B) may be a polymerderived from a fluoroalkyl group-containing monomer such as afluoroalkyl group-containing (meth)acrylate, a fluoroalkylgroup-containing maleate or fumarate, and a fluoroalkyl group-containingurethane.

[0025] The fluorine-containing polymer (A) may be, for example, apolymer comprising:

[0026] (A-I) a repeat unit derived from a monomer having a fluoroalkylgroup, and

[0027] (A-II) a repeat unit derived from vinyl chloride and/orvinylidene chloride. An example of the fluorine-containing polymer (A)is a copolymer comprising:

[0028] (A-I) a repeat unit derived from a monomer having a fluoroalkylgroup,

[0029] (A-II) a repeat unit derived from vinyl chloride and/orvinylidene chloride,

[0030] (A-III) a repeat unit derived from a fluorine-free monomer, and

[0031] (A-IV) a repeat unit derived from a crosslinkable monomer.

[0032] The fluorine-containing polymer (B) may be, for example, acopolymer which comprises

[0033] (B-I) a repeat unit derived from a monomer having a fluoroalkylgroup, and which does not comprise a repeat unit derived from vinylchloride and/or vinylidene chloride. An example of thefluorine-containing polymer (B) is a copolymer which comprises:

[0034] (B-I) a repeat unit derived from a monomer having a fluoroalkylgroup,

[0035] (B-II) a repeat unit derived from a fluorine-free monomer, and

[0036] (B-III) a repeat unit derived from a crosslinkable monomer, andwhich does not comprise a repeat unit derived from vinyl chloride and/orvinylidene chloride.

[0037] The repeat units (A-I) and (B-I) are preferably a repeat unitderived from a (meth)acrylate ester having a fluoroalkyl group.

[0038] The fluoroalkyl group-containing (meth)acrylate ester may be ofthe formula:

Rf—A—OCOCR¹¹═CH₂

[0039] wherein Rf is a fluoroalkyl group having 3 to 21 carbon atoms,R¹¹ is a hydrogen atom or a methyl group, and A is a divalent organicgroup.

[0040] In the above formula, A may be a linear or branched alkylenegroup having 1 to 20 carbon atoms, a —SO₂N(R²¹)R²²— group or a—CH₂CH(OR²³)CH₂— group (R²¹ is an alkyl group having 1 to 10 carbonatoms, R²² is a linear or branched alkylene group having 1 to 10 carbonatoms, and R²³ is a hydrogen atom or an acyl group having 1 to 10 carbonatoms).

[0041] Examples of the fluoroalkyl group-containing (meth)acrylate areas follows:

 Rf—(CH₂)_(n)OCOCR³═CH₂  (2)

[0042]

 Rf—O—Ar—CH₂OCOCR³═CH₂  (6)

[0043] wherein Rf is a fluoroalkyl group having 3 to 21 carbon atoms, R¹is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R² isan alkylene group having 1 to 10 carbon atoms, R³ is a hydrogen atom ora methyl group, and Ar is arylene group optionally having a substituent,and n is an integer of 1 to 10.

[0044] Specific examples of the fluoroalkyl group-containing(meth)acrylate are as follows:

[0045] CF₃(CF₂)₇(CH₂)₁₀OCOCH═CH₂

[0046] CF₃(CF₂)₇(CH₂)₁₀OCOC(CH₃)═CH₂

[0047] CF₃(CF₂)₆CH₂OCOCH═CH₂

[0048] CF₃(CF₂)₈CH₂OCOC(CH₃)═CH₂

[0049] (CF₃)₂CF(CF₂)₆(CH₂)₂OCOCH═CH₂

[0050] (CF₃)₂CF(CF₂)₈(CH₂)₂OCOCH═CH₂

[0051] (CF₃)₂CF(CF₂)₁₀(CH₂)₂OCOCH═CH₂

[0052] (CF₃)₂CF(CF₂)₆(CH₂)₂OCOC(CH₃)═CH₂

[0053] (CF₃)₂CF(CF₂)₈(CH₂)₂OCOC(CH₃)═CH₂

[0054] (CF₃)₂CF(CF₂)₁₀(CH₂)₂OCOC(CH₃)═CH₂

[0055] CF₃CF₂(CF₂)₆(CH₂)₂OCOCH═CH₂

[0056] CF₃CF₂(CF₂)₈(CH₂)₂OCOCH═CH₂

[0057] CF₃CF₂(CF₂)₁₀(CH₂)₂OCOCH═CH₂

[0058] CF₃CF₂(CF₂)₆(CH₂)₂OCOC(CH₃)═CH₂

[0059] CF₃CF₂(CF₂)₈(CH₂)₂OCOC(CH₃)═CH₂

[0060] CF₃CF₂(CF₂)₁₀(CH₂)₂OCOC(CH₃)═CH₂

[0061] CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOCH═CH₂

[0062] CF₃(CF₂)₇SO₂N (C₂H₅)(CH₂)₂OCOCH═CH₂

[0063] (CF₃)₂CF(CF₂)₈CH₂CH(OCOCH₃) CH₂OCOC(CH₃)═CH₂

[0064] (CF₃)₂CF(CF₂)₆CH₂CH(OH)CH₂OCOCH═CH₂

[0065] The repeat units (A-III) and (B-II) are preferably derived from afluorine-free vinyl monomer. Non-limiting examples of preferable monomerconstituting the repeat units (A-III) and (B-II) include, for example,ethylene, vinyl acetate, acrylonitrile, styrene, alkyl (meth)acrylate,polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate,methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol(meth)acrylate, vinyl alkyl ether and isoprene.

[0066] The monomer constituting the repeat units (A-III) and (B-II) maybe a (meth)acrylate ester having an alkyl group. The number of carbonatoms of the alkyl group may be from 1 to 30, for example, from 6 to 30,e.g., from 10 to 30. For example, the monomer constituting the repeatunits (A-III) and (B-II) may be acrylates of the general formula:

CH₂═CA¹COOA²

[0067] wherein A¹ is a hydrogen atom or a methyl group, and A² is analkyl group of C_(n)H_(2n+1) (n=1 to 30). The copolymerization with thismonomer can improve various properties such as water- and oil-repellencyand soil releasability; cleaning durability, washing durability andabrasion resistance of said repellency and releasability; solubility insolvent; hardness; and feeling, according to necessity.

[0068] The crosslinkable monomer constituting the repeat units (A-IV)and (B-III) may be a fluorine-free vinyl monomer having at least tworeactive groups. The crosslinkable monomer may be a compound having atleast two carbon-carbon double bonds, or a compound having at least onecarbon-carbon double bond and at least one reactive group.

[0069] Examples of the crosslinkable monomer includediacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide,hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate,3-chloro-2-hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene,chloroprene and glycidyl (meth)acrylate, to which the crosslinkablemonomer is not limited. The copolymerization with this monomer canimprove various properties such as water- and oil-repellency and soilreleasability; cleaning durability and washing durability of saidrepellency and releasability; solubility in solvent; hardness; andfeeling, according to necessity.

[0070] The fluorine-containing polymer (A) and the fluorine-containingpolymer (B) preferably has a weight average molecular weight of 2,000 to1,000,000, for example, 10,000 to 200,000.

[0071] Preferably, the amount of the repeat unit (A-I) is from 40 to89.9% by weight, more preferably from 50 to 79.5% by weight,

[0072] the amount of the repeat unit (A-II) is from 5 to 50% by weight,more preferably from 10 to 40% by weight,

[0073] the amount of the repeat unit (A-III) is from 5 to 54.9% byweight, more preferably from 10 to 40% by weight, and

[0074] the amount of the repeat unit (A-IV) is from 0.1 to 10% byweight, more preferably 0.5 to 5% by weight,

[0075] based on the fluorine-containing polymer (A).

[0076] Preferably, the amount of the repeat unit (B-I) is from 39 to94.9% by weight, more preferably from 50 to 89.5% by weight,

[0077] the amount of the repeat unit (B-II) is from 5 to 60% by weight,more preferably from 10 to 40% by weight, and

[0078] the amount of the repeat unit (B-III) is from 0.1 to 10% byweight, more preferably from 0.5 to 5% by weight,

[0079] based on the fluorine-containing polymer (B).

[0080] A weight ratio of the fluorine-containing polymer (A) tofluorine-containing polymer (B) in this mixture may be from 1:99 to99:1, for example, from 10:90 to 90:10, particularly from 70:30 to90:10.

[0081] The fluorine-containing polymer (A) and (B) in the presentinvention can be produced by any polymerization method, and theconditions of the polymerization reaction can be arbitrary selected. Thepolymerization method includes, for example, solution polymerization andemulsion polymerization. Among them, emulsion polymerization isparticularly preferred.

[0082] The method of producing the fluorine-containing polymer (A) isexplained hereinafter.

[0083] In the solution polymerization, there can be used a method ofdissolving a monomer (A-I), a monomer (A-III) and a crosslinking monomer(A-IV) in an organic solvent in the presence of a polymerizationinitiator, replacing the atmosphere by nitrogen, charging vinyl chlorideand/or vinylidene chloride (A-II) and stirring the mixture with heatingat the temperature within the range from 50° C. to 120° C. for 1 hour to10 hours. Examples of the polymerization initiator includeazobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, laurylperoxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropylperoxydicarbonate. The polymerization initiator is used in the amountwithin the range from 0.01 to 5 parts by weight based on 100 parts byweight of the monomers.

[0084] The organic solvent is inert to the monomer and dissolves them,and examples thereof include pentane, hexane, heptane, octane,cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran,1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate,butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane,trichloroethylene, perchloroethylene, tetrachlorodifluoroethane andtrichlorotrifluoroethane. The organic solvent may be used in the amountwithin the range from 50 to 1,000 parts by weight based on 100 parts byweight of the monomers (A-I) to (A-IV).

[0085] In the emulsion polymerization, there can be used a method ofemulsifying a monomer (A-I), a monomer (A-III) and a crosslinkingmonomer (A-IV) in water in the presence of a polymerization initiatorand an emulsifying agent, replacing the atmosphere by nitrogen, chargingvinyl chloride and/or vinylidene chloride (A-II) and copolymerizing withstirring at the temperature within the range, for example, from 50° C.to 80° C. for 1 hour to 10 hours. As the polymerization initiator, forexample, water-soluble initiators (e.g., benzoyl peroxide, lauroylperoxide, L-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide,3-carboxypropionyl peroxide, acetyl peroxide, azobisisohtitylamidinedihydrochloride, azobisisobutyronitrile, sodium peroxide, potassiumpersulfate and ammonium persulfate) and oil-soluble initiators (e.g.,azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, laurylperoxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropylperoxydicarbonate) are used. The polymerization initiator is used in theamount within the range from 0.01 to 5 parts by weight based on 100parts by weight of the monomers.

[0086] In order to obtain a copolymer dispersion ill water, which issuperior in storage stability, it is desirable that the monomers areatomized in water by using an emulsifying device capable of applying astrong shattering energy (e.g., a high-pressure homogenizer and anultrasonic homogenizer) and then polymerized with using the oil-solublepolymerization initiator. As the emulsifying agent, various emulsifyingagents such as an anionic emulsifying agent, a cationic emulsifyingagent and a nonionic emulsifying agent can be used in the amount withinthe range from 0.5 to 10 parts by weight based on 100 parts by weight ofthe monomers. When the monomers (A-I) to (A-IV) are not completelycompatibilized, a compatibilizing agent capable of sufficientlycompatibilizing them (e.g., a water-soluble organic solvent and alow-molecular weight monomer) is preferably added to these monomers. Bythe addition of the compatibilizing agent, the emulsifiability andcopolymerizability can be improved.

[0087] Examples of the water-soluble organic solvent include acetone,methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycolmonomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.The water-soluble organic solvent may be used in the amount within therange from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight,based on 100 parts by weight of water.

[0088] The fluorine-containing polymer (B) can be prepared in the samemanner as in the fluorine-containing polymer (A), except that vinylchloride or vinylidene chloride is not used.

[0089] A liquid containing the fluorine-containing polymer (A) and aliquid containing the fluorine-containing polymer (B), which areseparately prepared, are mixed and optionally a medium (for example,water or an organic solvent) is added to give the water- andoil-repellent agent.

[0090] The substrate to be treated in the present invention ispreferably a textile, particularly a carpet. The textile includesvarious examples. Examples of the textile include animal- orvegetable-origin natural fibers such as cotton, hemp, wool and silk;synthetic fibers such as polyamide, polyester, polyvinyl alcohol,polyacrylonitrile, polyvinyl chloride and polypropylene; semisyntheticfibers such as rayon and acetate; inorganic fibers such as glass fiber,carbon fiber and asbestos fiber; and a mixture of these fibers. Thepresent invention can be suitably used in carpets made of nylon fibers,polypropylene fibers and/or polyester fibers, because the presentinvention provides excellent resistance to a detergent solution andbrushing (mechanical).

[0091] The textile may be in any form such as a fiber and a fabric. Whenthe carpet is treated with the water- and oil-repellent agent, thecarpet may be formed after the fibers or yarns are treated with thewater- and oil-repellent agent, or the formed carpet may be treated withthe water- and oil-repellent agent. Examples of the substrate to betreated include glass, paper, wood, leather, fur, asbestos, brick,cement, metal and oxide, ceramics, plastic, coated surface and plaster,in addition to the textile.

EXAMPLES

[0092] The following Examples further illustrate the present inventionin detail but are not to be construed to limit the scope thereof. Thewater repellency, oil repellency, soil releasability and fluorineadhesion amount of the carpets obtained in the Examples and ComparativeExample were evaluated.

[0093] Test procedures of the water repellency, the oil repellency, thesoil releasability, fluorine adhesion amount and cleaning are asfollows.

[0094] (1) Water repellency

[0095] A droplet of a isopropyl alcohol (IPA)/water mixture liquid shownin Table 1 is softly positioned on a carpet surface, and a maximumcontent of IPA (% by volume) in the liquid which maintains the dropletshape is taken as the result of the water repellency.

[0096] Specific procedure is as follows.

[0097] A carpet treated for giving repellency is stored in atherio-hyqrostat having a temperature of 21° C. and a humidity of 65%for at least 4 hours. A test liquid (having the composition shown inTable 1) which has been also stored at 21° C. is used. The temperatureof a measurement room is controlled to be 21° C. Droplets of the testliquid in an amount of 50 μL are softly dropped by a micropipette on thecarpet and the diameter of the droplets is 5 mm. The micropippete isvertically stood and droplets are softly dropped. Five droplets arepositioned. If 4 or 5 droplets remain on the carpet after standing for10 seconds, it is evaluated that the test liquid passes the test. Themaximum content of IPA (% by volume) in the test liquid which passes thetest is taken as the result of the water repellency. TABLE 1 Mixingcomposition (% by volume) Isopropyl alcohol Water 100 0 90 10 80 20 7030 60 40 50 50 40 60 30 70 25 75 20 80 15 85 10 90 5 95 2 98 0 100

[0098] (2) Oil repellency

[0099] According to AATCC-TM-118-1992, five droplets of the testsolution shown in Table 2 are positioned on a carpet and the penetrationstate after 30 seconds is observed. A maximum point corresponding to thetest solution, four droplets of which exhibit no penetration, is takenas the oil repellency. TABLE 2 Surface tension Point Test solution(mN/m, 25° C.) 0 Inferior to 1 — 1 Nujol 31.2 2 Mixture liquid of 29.6n-Hexadecane (35 wt. parts)/ nujol (65 wt. parts) 3 n-Hexadecane 27.3 4n-Tetradecane 26.7 5 n-Dodecane 25.0 6 n-Decane 23.5

[0100] (3) Soil releasability (Stain proof property)

[0101] A carpet sample piece (size: 18.2 cm in a direction of tufting,and 8.9 cm in a direction perpendicular to a tufting direction) treatedwith a water- and oil-repellent agent and a blank carpet piece (size:18.2 cm in direction of tufting, and 8.9 cm in a direction perpendicularto tufting direction) are kept to stand for at least 4 hours in anatmosphere of 21° C. and 65% RH. Before the soil releasability test, L*,a* and b* of the carpet pieces are measured at five spots. Two carpetpieces are adhered with a double-sided tape to an internal surface of apot of a ball mill. 10 g of dry soil (artificial soil having thecomposition shown in Table 3, dried in a desiccator for at least 48hours) is charged in the pot and then a lid is put on the pot. The potis slightly shaken so that the dry soil is positioned almost uniformlyon the carpet test piece. The lid of the pot is taken off, the carpetsamples are removed, and then 50 ceramic balls (according to AATCC TestMethod 123-1989) are charged into the pot, and the lid is firmly put onthe pot. In the ball mill apparatus, the pot is rotated at 80 rpm for 7minutes and 30 seconds. The lid of the pot is taken off, the carpetsamples are removed, and then the double-sided tapes are peeled off.Excess dry soil on a front surface of the carpet test piece is removedby a vacuum cleaner. The vacuum cleaner is applied to the front surfacein each direction (longitudinal and transverse directions) for back andforth five times. Finally, the vacuum cleaner is applied also to theback surface for back and force once. L*, a* and b* of each carpet piecewithout excess dry soil are measured at five spots by a color differencemeter (CR-310 manufactured by MINOLTA Co., Ltd., having a circulardetection part having the diameter of 50 mm).

[0102] A color difference (AE*ab) of the carpet surface is calculatedaccording to the following equation from L*, a* and b* before soilreleasability test and L*, a* and b* after soil releasability test.Since the measurement for each carpet sample is conducted at five spots,the calculation is conducted by using a value at the same spot.

ΔE*ab=[(ΔL*)²+(Δa*)²+(Δb*)²]^(½)

[0103] ΔL*: difference of L* before and after soil releasability test

[0104] Δa*; difference of a* before and after soil releasability test

[0105] Δb*. difference of b* before and after soil releasability test

[0106] An average of ΔE*ab is determined for each carpet test sample,and this average is taken as ΔE, which is a result of soilreleasability. TABLE 3 Components of artificial soil Amount (wt %) Peatmoss (dark) 38.4 Portland cement 18 Kaolin clay 18 Silica (200 mesh) 18Carbon black 1.05 Red iron oxide 0.30 Mineral oil 6.25

[0107] (4) Adhesion amount of fluorine

[0108] The content of fluorine (ppm) present on a carpet fiber after theExhaust treatment is measured by an oxygen combustion method.

[0109] (5) Cleaning

[0110] A carpet fabric treated with a water- and oil-repellent agent iscleaned according to AATCC-TM-171-1995. The detail of the cleaningprocedure is as follows. A carpet piece having a size of 8.9 cm×18.2 cmis fixed on a test pedestal. A steam cleaner (having functions ofsuction and warm water injection) is applied to the carpet surface fromback and forth once, with suction and spraying of 60° C. water, and thenapplied to the carpet surface from back and forth once, with suctionalone. The above procedure is defined as once of the cleaning. After agiven number of times of the cleaning is conducted, the carpet is driedat 105° C. for 15 minutes in hot-air dryer to complete the cleaning.

[0111] The water repellency, the oil repellency, the soil releasabilityand the fluorine adhesion amount are measured before and after thecleaning.

[0112] The carpet of the present invention preferably has the waterrepellency of at least 90 and the oil repellency of at least 5 beforethe cleaning, and the water repellency of at least 40 and the oilrepellency of at least 2 after 10 times of the cleaning.

Preparative Example 1 Preparation of (a) a Fluorine-containing Water-and Oil-repellent Agent Containing Vinyl Chloride

[0113] CH₂═CHCOO(CH₂)₂(CF₂CF₂)_(n)CF₂CF₃ (a mixture of compounds whereinn is 3, 4 and 5 in a weight ratio of 5:3:1) (FA), stearyl acrylate(StA), N-methylolacrylamide (N-MAM), 3-chloro-2-hydroxypropylmethacrylate (TOPOLEN M), deionized water, n-laurylmercaptan (LSH, achain transfer agent), octadecyltrimethyl ammonium chloride (CATION2ABT, a cationic emulsifier), polyoxyethylenealkylphenyl ether (EMULGEN985, a nonionic emulsifier), polyoxyethylene-alkylphenyl ether (NONIONHS-208, a nonionic emulsifier), sorbitan monopalmitate (NONION PP-40R, anonionic emulsifier) and dipropyleneglycol monomethyl ether (DPM) weremixed in the amounts shown in Table 4 to give a mixture liquid.

[0114] This mixture liquid was heated at 60° C. and emulsified by a highpressure homogenizer. The resultant emulsion was charged into a 1 Lautoclave and subjected to a nitrogen gas replacement to remove adissolved oxygen. Vinyl chloride having a purity of 99% (VCl) wascharged in the amount shown in Table 4 and then an initiator,azobisamide dipropane (V-50) was charged in the amount shown in Table 4.With stirring, the copolymerization reaction was conducted for 60° C. at8 hours to give a vinyl chloride-containing copolymer emulsion, whichwas diluted with water to give an emulsion having a solid content of 30%by weight.

Preparative Example 2 Preparation of (b) a Fluorine-containing Water-and Oil-repellent Agent Free of Vinyl Chloride

[0115] CH₂═CHCOO(CH₂)₂(CF₂CF₂)_(n)CF₂CF₃ (a mixture of compounds whereinn is 3, 4 and 5 in a weight ratio of 5:3:1) (FA), stearyl acrylate(StA), 2-hydroxyethyl methacrylate (2ERA), glycidyl methacrylate(BLENMER G), N-methylolacrylamide (N-MAM), 3-chloro-2-hydroxypropylmethacrylate (TOPOLEN M), deionized water, n-laurylmercaptan (LSH),polyoxyethylene-alkylphenyl ether sulfate ammonium (HITENOL N-17, ananionic emulsifier), polyoxyethylenealkylphenyl ether (NONION HS-220, anonionic emulsifier), sorbitan monolaurate (LP-20R, a nonionicemulsifier) and dipropylene glycol monomethylether (DPM) were mixed inthe amounts shown in Table 4 to give a mixture liquid.

[0116] This mixture liquid was heated at 60° C. and emulsified by a highpressure homogenizer. The resultant emulsion was charged into a 1 Lautoclave and subjected to a nitrogen gas replacement to remove adissolved oxygen. Then, an initiator, ammonium persulfate (APS) wascharged in the amount shown in Table 4. With stirring, thecopolymerization reaction was conducted for 60° C. at 8 hours to give afluorine-containing copolymer emulsion, which was diluted with water togive an emulsion having a solid content of 30% by weight. TABLE 3Composition ratio of charged monomers (weight (g)) Pre. Pre. Ex. 1 Ex. 2SFA 90.4 79.2 STA 6.0 19.1 VCl (vinyl chloride) 14.7 — 2EHA — 19.1BLENMER G — 2.6 N-MAM 2.4 3.0 TOPOLEN M 0.6 1.3 LSH 0.8 0.24 Ammoniumpersulfate — 0.56 azobisamide dipropane 0.76 NONION PP-40R 1.92 — NONIONHS-208 4.20 — NONION HS-220 — 1.72 LP-20R — 2.16 EMULGEN 985 1.92 —CTION 2ABT 2.0 — HITENOL N-17 — 5.20 Pure water 236 244

Example 1

[0117] 0.9 Grams of a mixture liquid of the fluorine-containing water-and oil-repellent agent (a) (which is a fluorine-containing water- andoil-repellent agent containing vinyl chloride) produced in PreparativeExample 1 and the fluorine-containing water- and oil-repellent agent (b)(which is a water- and oil-repellent agent free of vinyl chloride)produced in Preparative Example 2 (the mixing weight ratio of 8 to 2 interms of solid) and 5 g of a stain blocking agent FX-657 (manufacturedby 3M) were diluted with water to 1,000 g to give a mixture liquid. Thesolid weight ratio of the water- and oil-repellent agent and the stainblocking agent was 1:5.6. The pH of the mixture liquid was adjusted to1.5 by adding a 10% aqueous solution of sulfamic acid to give atreatment liquid.

[0118] A carpet (8.9 cm×18.2 cm, nylon 6,6, cut piled, density: 36oz/yd²) was immersed in the treatment liquid for 30 seconds. Then, thecarpet was squeezed to give the WPU (wet pick up) of 300%. Then, anormal pressure steamer treatment (the temperature of 100° C. to 107°C.) was conducted for 90 seconds under the state that a pile surface ofthe carpet is upward. Then, the carpet was lightly rinsed with 2 L ofwater, and centrifugally dehydrated to give the WPU of about 25%.Finally, the carpet was thermally cured at 110° C. for ten minutes.Then, this carpet was cleaned (five times or ten times). The waterrepellency, the oil repellency, the soil releasability and the fluorineadhesion amount were evaluated before and after the cleaning. Theresults are shown in Tables A to D.

Comparative Example 1

[0119] 0.8 Grams of the fluorine-containing water- and oil repellentagent (a) and 5 g of the stain blocking agent FX-657 (manufactured by3M) were diluted with water to 1,000 g to give a mixture liquid. Thesolid weight ratio of the water- and oil-repellent agent and the stainblocking agent was 1:6.3. The pH of the mixture liquid was adjusted to1.5 by adding a 10% aqueous solution of sulfamic acid. Then, thetreatment and evaluation were conducted in the same manner as inExample 1. The results are shown in Tables A to D.

Comparative Example 2

[0120] 1.0 Grams of the fluorine-containing water- and oil repellentagent (b) and 5 g of the stain blocking agent FX-657 (manufactured by3M) were diluted with water to 1,000 g to give a mixture liquid. Thesolid weight ratio of the water- and oil-repellent agent and the stainblocking agent was 1:5. The pH of the mixture liquid was adjusted to 1.5by adding a 10% aqueous solution of sulfamic acid. Then, the treatmentand evaluation were conducted in the same manner as in Example 1. Theresults are shown in Tables A to D.

Comparative Example 3

[0121] 5.7 Grams of a commercially available emulsion repellent agent(solid concentration: 21% by weight) [a mixture of a fluorine-containingoil repellent agent containing chlorine (6% by weight) and a stainblocking agent (a phenol-formaldehyde condensation product) (15% byweight)] was diluted with water to 1,000 g to give a mixture liquid. ThepH of the mixture liquid was adjusted to 1.5 by adding a 10% aqueoussolution of sulfamic acid. Then, the treatment and evaluation wereconducted in the same manner as in Comparative Example 1. The resultsare shown in Tables A to D.

Comparative Example 4

[0122] 5.7 Grams of a commercially available emulsion repellent agent(solid concentration: 21% by weight) [a mixture of a fluorine-containingoil repellent agent containing chlorine (6% by weight) and a stainblocking agent (a phenol-formaldehyde condensation product) (15% byweight)] and 12.5 g of MgSO₄ were diluted with water to 1,000 g to givea mixture liquid. The pH of the mixture liquid was adjusted to 1.5 byadding a 10% aqueous solution of sulfamic acid. Then, the treatment andevaluation were conducted in the same manner as in ComparativeExample 1. The results are shown in Tables A to D. TABLE A Results ofwater repellency evaluation Number of times Com. Com. Com. Com. ofcleaning Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 0 90 80 100 X 40 5 90 70 90 X 3010 40 40 40 X 30

[0123] TABLE B Results of oil repellency evaluation Number of times Com.Com. Com. Com. of cleaning Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 0 5 3 6 0 5 5 42 6 0 4 10 2 0 4 0 4

[0124] TABLE C Results of soil releasability (delta E value) Number oftimes Com. Com. Com. Com. of cleaning Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 016.5 16.5 19.8 24.9 18.9 5 18.0 16.7 21.7 25.7 19.6 10 19.5 19.6 22.825.1 21.1

[0125] TABLE D Results of fluorine adhesion amount measurement (ppm)Number of times Com. Com. Com. Com. of cleaning Ex. 1 Ex. 1 Ex. 2 Ex. 3Ex. 4 0 292 273 300 10 259 5 285 262 300 9 225 10 235 173 279 8 216

1. A method of preparing a treated textile, comprising steps of: (1)preparing a treatment liquid comprising a water- and oil-repellentagent, (2) adjusting pH of the treatment liquid to at most 7, preferablyat most 2, (3) applying the treatment liquid to the textile, (4)thermally treating the textile with steam, and (5) washing the textilewith water and dehydrating the textile, wherein the water- andoil-repellent agent comprises a combination of (A) a fluorine-containingpolymer comprising a repeat unit derived from vinyl chloride and/orvinylidene chloride, and (B) a fluorine-containing polymer free from arepeat unit derived from vinyl chloride and/or vinylidene chloride. 2.The method according to claim 1, wherein the fluorine-containing polymer(A) comprises: (A-I) a repeat unit derived from a monomer having afluoroalkyl group, and (A-II) a repeat unit derived from vinyl chlorideand/or vinylidene chloride.
 3. The method according to claim 1, whereinthe fluorine-containing polymer (A) comprises: (A-I) a repeat unitderived from a monomer having a fluoroalkyl group, (A-II) a repeat unitderived from vinyl chloride and/or vinylidene chloride, (A-III) a repeatunit derived from a fluorine-free monomer, and (A-IV) a repeat unitderived from a crosslinkable monomer.
 4. The method according to claim1, wherein the fluorine-containing polymer (B) comprises (B-I) a repeatunit derived from a monomer having a fluoroalkyl group, and does notcomprise a repeat unit derived from vinyl chloride and/or vinylidenechloride.
 5. The method according to claim 1, wherein thefluorine-containing polymer (B) comprises: (B-I) a repeat unit derivedfrom a monomer having a fluoroalkyl group, (B-II) a repeat unit derivedfrom a fluorine-free monomer, and (B-III) a repeat unit derived from acrosslinkable monomer, and does not comprise a repeat unit derived fromvinyl chloride and/or vinylidene chloride.
 6. A textile obtainable bythe method according to claim
 1. 7. A carpet obtainable by the methodaccording to claim
 1. 8. The carpet according to claim 7, wherein thecarpet comprises a nylon fiber, a propylene fiber and/or a polyesterfiber.
 9. The carpet according to claim 7, which has the waterrepellency of at least 90 and the oil repellency of at least 5 beforethe cleaning, and the water repellency of at least 40 and the oilrepellency of at least 2 after 10 times of the cleaning, wherein thenumerical value of the water repellency is a maximum content of IPA (%by volume) in a test solution resulting from the test that five dropletsof an isopropyl alcohol (IPA)/water mixture test solution are softlypositioned on a carpet surface, the penetration state of the dropletsafter 10 seconds are observed and at least four droplets do not exhibitthe penetration, and the numerical value of the oil repellency is amaximum value of oil repellency according to AATCC-TM-118-1992 resultingfrom the test that five droplets of a test solution are softlypositioned on a carpet surface, the penetration state of the dropletsafter 30 seconds are observed and at least four droplets do not exhibitthe penetration.
 10. A water- and oil-repellent agent used in a methodof preparing a treated textile, comprising steps of: (1) preparing atreatment liquid comprising a water- and oil-repellent agent, (2)adjusting pH of the treatment liquid to at most 7, preferably at most 2,(3) applying the treatment liquid to the textile, (4) thermally treatingthe textile, and (5) washing the textile with water and dehydrating thetextile, wherein the water- and oil-repellent agent comprises acombination of (A) a fluorine-containing polymer comprising a repeatunit derived from vinyl chloride and/or vinylidene chloride, and (B) afluorine-containing polymer free from a repeat unit derived from vinylchloride and/or vinylidene chloride.